JPH11256338A - Production of gas barrier film - Google Patents
Production of gas barrier filmInfo
- Publication number
- JPH11256338A JPH11256338A JP5946498A JP5946498A JPH11256338A JP H11256338 A JPH11256338 A JP H11256338A JP 5946498 A JP5946498 A JP 5946498A JP 5946498 A JP5946498 A JP 5946498A JP H11256338 A JPH11256338 A JP H11256338A
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- Prior art keywords
- film
- gas barrier
- plasma
- treatment
- thin film
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はガスバリア性フィル
ム、特に酸素バリア性及び／又は水蒸気バリア性に優れ
たガスバリア性フィルムの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a gas barrier film, particularly a gas barrier film having excellent oxygen barrier properties and / or excellent water vapor barrier properties.
【０００２】[0002]
【従来の技術】従来、ガスバリア性に優れたフィルムと
して、各種フィルム上にアルミニウムを積層したもの、
ポリビニリデン樹脂やポリビニリデンポリアクリル酸共
重合体樹脂をコーティングしたもの、あるいはＳｉＯｘ
等の薄膜をコーティングしたものなどが知られている。
これらのうちＳｉＯｘ等の薄膜を形成させたガスバリア
性フィルムの製造方法としては、各種フィルム上に真空
蒸着、スパッタリング、イオンプレーティング、減圧プ
ラズマＣＶＤ等の方法が挙げられる。真空蒸着法による
高分子フィルム上への酸化珪素薄膜の好ましい製造方法
としては、金属を加熱して気相で酸素と反応させる反応
蒸着法、電子線により酸化珪素を蒸着源とする電子ビー
ム蒸着法、珪素又は酸化珪素を加熱し、必要に応じて気
相で酸素と反応させる電子ビーム反応蒸着法がある。ま
た、減圧プラズマＣＶＤ法によるガスバリア性フィルム
の製造方法としては、原料の有機珪素化合物をプラズマ
中に導入することにより無機の酸化珪素とする方法がよ
く知られている。このとき原料として使用される有機珪
素化合物として具体的には、テトラエトキシシラン、メ
チルトリエトキシシラン、ヘキサメチルジシロキサン、
テトラメトキシシラン、メトキシトリメチルシラン、テ
トラメチルシラン、トリフェニルシラン、ヘキサメチル
トリシロキサン、テトラクロロシラン、トリクロロメチ
ルシラン、トリメチルクロロシラン、ジメチルジクロロ
シラン、ジメチルクロロシランなどが挙げられる。2. Description of the Related Art Conventionally, as a film having excellent gas barrier properties, aluminum is laminated on various films,
Coated with polyvinylidene resin or polyvinylidene polyacrylic acid copolymer resin, or SiOx
And the like are known.
Among them, examples of a method for producing a gas barrier film having a thin film such as SiOx formed thereon include methods such as vacuum deposition, sputtering, ion plating, and low-pressure plasma CVD on various films. Preferred methods for producing a silicon oxide thin film on a polymer film by a vacuum vapor deposition method include a reactive vapor deposition method in which a metal is heated and reacted with oxygen in a gas phase, and an electron beam vapor deposition method in which silicon oxide is used as a vapor deposition source by an electron beam. There is an electron beam reactive evaporation method in which silicon or silicon oxide is heated and, if necessary, is reacted with oxygen in a gas phase. Further, as a method for producing a gas barrier film by a low-pressure plasma CVD method, a method of introducing an organic silicon compound as a raw material into plasma to obtain inorganic silicon oxide is well known. At this time, as the organic silicon compound used as a raw material, specifically, tetraethoxysilane, methyltriethoxysilane, hexamethyldisiloxane,
Examples include tetramethoxysilane, methoxytrimethylsilane, tetramethylsilane, triphenylsilane, hexamethyltrisiloxane, tetrachlorosilane, trichloromethylsilane, trimethylchlorosilane, dimethyldichlorosilane, and dimethylchlorosilane.
【０００３】[0003]
【発明が解決しようとする課題】前記の従来技術のうち
真空蒸着、スパッタリング又はイオンプレーティングに
よる方法はいずれも固体の原料を使用するため、操作性
が悪かったり、原料が高価で経済性が悪いという問題点
を有している。また、いずれの方法も１０-1Ｔｏｒｒ以
上の高い真空度を要する真空プロセスであるため、減圧
用の真空設備が必要であったり、真空度に見合ったシー
ル性を確保する必要があるため、設備コスト（イニシャ
ルコスト）やランニングコストが高いという問題点があ
る。本発明はこのような従来技術の問題点を解決し、酸
素ガスバリア性及び水蒸気バリア性に優れ、透明性も高
く、さらに安定した品質のガスバリア性フィルムを、高
度の真空設備を必要としない大気圧下のプロセスで操作
性よく容易に製造することができるガスバリア性フィル
ムの製造方法を提供することを目的とする。Among the above-mentioned prior arts, the methods using vacuum deposition, sputtering or ion plating all use solid raw materials, so that their operability is poor, and the raw materials are expensive and economical. There is a problem that. In addition, since each of these methods is a vacuum process requiring a high degree of vacuum of 10 -1 Torr or more, vacuum equipment for decompression is required, or it is necessary to secure sealing properties corresponding to the degree of vacuum. There is a problem that cost (initial cost) and running cost are high. The present invention solves such problems of the prior art, and provides a gas barrier film having excellent oxygen gas barrier properties and water vapor barrier properties, high transparency, and stable quality at atmospheric pressure which does not require advanced vacuum equipment. An object of the present invention is to provide a method for producing a gas barrier film that can be easily produced with good operability by the following process.
【０００４】[0004]
【課題を解決するための手段】本発明は高分子フィルム
上に、２０〜１５０℃の温度域において液体である有機
珪素化合物を原料として、６００〜１５２０Ｔｏｒｒの
圧力下で発生するプラズマを用いたＣＶＤ法により、Ｓ
ｉＯｘ（ｘ＝１．０〜２．０）で表される酸化珪素を主
成分とする薄膜を形成させることを特徴とするガスバリ
ア性フィルムの製造方法である。According to the present invention, there is provided a CVD method using a plasma generated on a polymer film at a pressure of 600 to 1520 Torr from an organic silicon compound which is a liquid in a temperature range of 20 to 150 ° C. By law, S
A method for manufacturing a gas barrier film, comprising forming a thin film containing silicon oxide represented by iOx (x = 1.0 to 2.0) as a main component.
【０００５】本発明の方法においては、酸化珪素を主成
分とする薄膜を形成させるに先立ち、高分子フィルム
に、該高分子フィルム表面に付着した汚れ物質の除去、
表面活性化のための前処理としてオゾン処理、紫外線処
理、コロナ放電やＡｒ、Ｈｅ、Ｎ2 、Ｏ2 等の単一又は
混合雰囲気下でのプラズマ処理を単独で又は複数種組み
合わせて施すのが好ましい。中でもＯ2 プラズマ処理が
好適である。また、酸化珪素を主成分とする薄膜を形成
させた後に、後処理としてＯ2 プラズマ処理を行うこと
により未反応原料の酸化を促進させ、コーティング膜の
組成をさらに均一化させることができる。[0005] In the method of the present invention, prior to forming a thin film containing silicon oxide as a main component, removing a contaminant attached to the surface of the polymer film,
Ozone treatment, ultraviolet treatment, corona discharge or plasma treatment under a single or mixed atmosphere of Ar, He, N 2 , O 2, etc. may be performed alone or in combination as a pretreatment for surface activation. preferable. Among them, O 2 plasma treatment is preferable. Further, after forming a thin film containing silicon oxide as a main component, by performing an O 2 plasma treatment as a post-treatment, the oxidation of the unreacted raw material is promoted, and the composition of the coating film can be further uniformed.
【０００６】[0006]
【発明の実施の形態】本発明の方法において、ガスバリ
ア性を有するコーティング膜の原料として使用する２０
〜１５０℃の温度域において液体である有機珪素化合物
とは、２０〜１５０℃の範囲内の少なくとも一部で液体
である化合物を意味し、具体的な化合物の例としてはテ
トラエトキシシラン、メチルトリエトキシシラン、ヘキ
サメチルジシロキサン、テトラメトキシシラン、メトキ
シトリメチルシラン、テトラメチルシラン、ヘキサメチ
ルトリシロキサン、テトラクロロシラン、トリクロロメ
チルシラン、トリメチルクロロシラン、ジメチルジクロ
ロシラン、ジメチルクロロシランなどを挙げることがで
きるが、特に好ましい化合物としてヘキサメチルジシロ
キサン（ＨＭＤＳＯ：Ｃ6 Ｈ18ＯＳｉ2 ：沸点１００
℃）がある。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, a material used as a raw material for a coating film having gas barrier properties is used.
The organic silicon compound which is liquid in a temperature range of from about 150 ° C. to about 150 ° C. means a compound which is liquid in at least a part of the range of from 20 ° C. to 150 ° C., and specific examples of the compound include tetraethoxysilane and methyltriethyl. Ethoxysilane, hexamethyldisiloxane, tetramethoxysilane, methoxytrimethylsilane, tetramethylsilane, hexamethyltrisiloxane, tetrachlorosilane, trichloromethylsilane, trimethylchlorosilane, dimethyldichlorosilane, dimethylchlorosilane, etc. As a preferred compound, hexamethyldisiloxane (HMDSO: C 6 H 18 OSi 2 : boiling point 100)
° C).
【０００７】本発明で基材として使用する高分子フィル
ムの例としてはポリエチレン、ポリプロピレン、ポリエ
チレンテレフタレート、ナイロン−６、ナイロン−６
６、ポリビニルアルコール等が挙げられる。これらの高
分子フィルムには添加剤、例えば可塑剤、帯電防止剤、
滑剤、紫外線吸収剤等が含まれていてもよい。Examples of the polymer film used as a substrate in the present invention include polyethylene, polypropylene, polyethylene terephthalate, nylon-6, nylon-6
6, polyvinyl alcohol and the like. Additives to these polymer films, such as plasticizers, antistatic agents,
A lubricant, an ultraviolet absorber and the like may be included.
【０００８】次に、本発明の方法によるガスバリア性フ
ィルムの一般的な製造方法を示す。先ず必要により、プ
ラズマＣＶＤ法による薄膜の形成に先立って、真空容器
中で高分子フィルムにコロナ放電処理、Ａｒ、Ｈｅ、Ｎ
2 、Ｏ2 などによるプラズマ処理等の前処理を施し、高
分子フィルムの汚れ物質の除去や表面の活性化を行う。
これによって、高分子フィルムとコーティング膜との接
着性を向上させることができる。処理条件は、それぞれ
の処理方法について、それぞれ最適条件を設定すればよ
いが、最も一般的な方法であるＯ2 プラズマ処理の標準
的な例を表１に示す。Next, a general method for producing a gas barrier film according to the method of the present invention will be described. First, if necessary, prior to the formation of a thin film by the plasma CVD method, a corona discharge treatment is applied to the polymer film in a vacuum vessel, and Ar, He, N
2. Pretreatment such as plasma treatment with O 2 is performed to remove contaminants and activate the surface of the polymer film.
Thereby, the adhesiveness between the polymer film and the coating film can be improved. The processing conditions may be set to optimal conditions for each processing method. Table 1 shows a standard example of O 2 plasma processing, which is the most general method.
【０００９】次いで、必要により前処理を施した高分子
フィルムに、前記の有機珪素化合物をＡｒ、Ｈｅなどの
不活性ガスをキャリアガスとして供給し、６００〜１５
２０Ｔｏｒｒ、好ましくは７６０±１０Ｔｏｒｒの大気
圧又はその近傍の圧力下で行う大気圧プラズマＣＶＤ法
によりコーティングを行い、高分子フィルム上にＳｉＯ
ｘ（ｘ＝１．０〜２．０）で表される酸化珪素を主成分
とする薄膜を形成させる。Next, the above-mentioned organosilicon compound is supplied as an inert gas such as Ar or He as a carrier gas to the polymer film which has been subjected to a pretreatment if necessary, and the resulting mixture is subjected to a heat treatment at 600 to 15 minutes.
Coating is performed by an atmospheric pressure plasma CVD method performed at or near an atmospheric pressure of 20 Torr, preferably 760 ± 10 Torr, and SiO 2 is coated on the polymer film.
A thin film mainly composed of silicon oxide represented by x (x = 1.0 to 2.0) is formed.
【００１０】本発明の方法における大気圧プラズマＣＶ
Ｄ法は、マッチングボックスを通して交流電源と接続さ
れる放電電極と接地電極を兼ねるロール型電極との間に
交流電界を印加し、６００〜１５２０Ｔｏｒｒの大気圧
又はその近傍の圧力下でグロー放電を発生させることが
可能な大気圧プラズマ処理装置を使用して、高分子フィ
ルム表面に操作性よく簡単にガスバリア性コーティング
膜を形成させる方法である。前記放電電極は導電体表面
に誘電体を被覆して形成したもので、誘電体としてはＡ
ｌ2 Ｏ3 が好適である。Atmospheric pressure plasma CV in the method of the present invention
In the method D, an AC electric field is applied between a discharge electrode connected to an AC power supply through a matching box and a roll-type electrode also serving as a ground electrode, and a glow discharge is generated under an atmospheric pressure of 600 to 1520 Torr or a pressure in the vicinity thereof. This is a method for easily forming a gas barrier coating film on the surface of a polymer film with good operability by using an atmospheric pressure plasma processing apparatus that can be used. The discharge electrode is formed by covering the surface of a conductor with a dielectric.
l 2 O 3 is preferred.
【００１１】ガスバリア性コーティング膜である酸化珪
素を主成分とする薄膜の厚み範囲は５〜２００ｎｍ、好
ましくは２０〜１３０ｎｍ、さらに好ましくは４０〜６
０ｎｍである。厚みが５ｎｍ未満ではガスバリア効果が
十分ではなく、また、２００ｎｍを超えると表面にクラ
ックを生じやすくなりバリア性が低下する。[0011] The thickness range of the thin film containing silicon oxide as a main component, which is a gas barrier coating film, ranges from 5 to 200 nm, preferably from 20 to 130 nm, and more preferably from 40 to 6 nm.
0 nm. If the thickness is less than 5 nm, the gas barrier effect is not sufficient, and if it exceeds 200 nm, cracks are likely to occur on the surface, and the barrier properties are reduced.
【００１２】さらに、大気圧プラズマＣＶＤ法による薄
膜の形成後に、後処理としてＯ2 プラズマ処理を行うこ
とにより未反応原料の酸化を促進させ、コーティング膜
の組成をさらに均一化させることができる。本発明にお
ける前処理、コーティング処理及び後処理の標準的な条
件を表１に示す。Further, after forming the thin film by the atmospheric pressure plasma CVD method, by performing O 2 plasma treatment as a post-treatment, the oxidation of the unreacted raw material is promoted, and the composition of the coating film can be made more uniform. Table 1 shows standard conditions of the pretreatment, the coating treatment, and the post-treatment in the present invention.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【実施例】以下実施例により本発明の方法をさらに具体
的に説明する。 （実施例１）図１は本発明方法を実施するための大気圧
プラズマ処理装置の概要を示す説明図である。幅１５０
ｍｍ、厚さ３０μｍの二軸延伸ＰＥＴ（ポリエチレンテ
レフタレート）フィルムを供試体として図１に示す形式
の試験装置を使用し、表２の条件でコーティングフィル
ムを作製し、性能評価を行った。作製した試料は表３に
示す試料Ｎｏ．１〜１０の１０種類である。EXAMPLES The method of the present invention will be described more specifically with reference to the following examples. (Embodiment 1) FIG. 1 is an explanatory view showing an outline of an atmospheric pressure plasma processing apparatus for carrying out the method of the present invention. Width 150
A biaxially stretched PET (polyethylene terephthalate) film having a thickness of 30 μm and a thickness of 30 μm was used as a test piece, and a coating film was prepared under the conditions shown in Table 2 using a test apparatus of the type shown in FIG. The manufactured samples are the sample Nos. Shown in Table 3. There are 10 types from 1 to 10.
【００１５】[0015]
【表２】 [Table 2]
【００１６】試験は先ず図１に示した装置のフィルム送
りロール９に処理を行う基材フィルム１６を装着し、フ
ィルム端部を張力調整用ロール１１、ロール型接地電極
４、張力調整用ロール１１を介してフィルム巻き取りロ
ール１０に固定する。放電電極３と冷却水により冷却し
ているロール型接地電極４（冷却系統は図示省略）との
距離を０．５〜２０ｍｍに各部での距離が等しくなるよ
うに調整した後、チャンバ５内を排気用の真空ポンプ６
を用いて０．１Ｔｏｒｒ程度まで排気した。次いでチャ
ンバ５内にＨｅガス導入管１７からＨｅガスを大気圧に
なるまで導入した。In the test, first, the base film 16 to be treated is mounted on the film feed roll 9 of the apparatus shown in FIG. 1, and the film ends are tension-adjusted roll 11, the roll-type ground electrode 4, and the tension-adjusted roll 11 And is fixed to the film take-up roll 10. After adjusting the distance between the discharge electrode 3 and the roll-type ground electrode 4 (cooling system not shown) cooled by the cooling water so that the distance in each part is equal to 0.5 to 20 mm, the inside of the chamber 5 is adjusted. Vacuum pump 6 for exhaust
The gas was evacuated to about 0.1 Torr by using. Next, He gas was introduced into the chamber 5 from the He gas introduction pipe 17 until the pressure became atmospheric pressure.
【００１７】図２は図１の大気圧プラズマ処理装置のプ
ラズマ処理部の拡大図である。図２に示すように放電電
極３は絶縁体２１に挟まれた導電体１９の表面を誘電体
２０で被覆した構造であり、電極間の距離が変わらない
ようロール型接地電極４に沿って湾曲した形状とし、導
入したガスが放電部に効率よく供給されるようなスリッ
ト部２２が形成されている。また、図示していないが冷
却水を通水できる構造となっている。FIG. 2 is an enlarged view of the plasma processing section of the atmospheric pressure plasma processing apparatus of FIG. As shown in FIG. 2, the discharge electrode 3 has a structure in which the surface of a conductor 19 sandwiched between insulators 21 is covered with a dielectric 20, and is curved along the roll-type ground electrode 4 so that the distance between the electrodes does not change. The slit 22 is formed such that the introduced gas is efficiently supplied to the discharge unit. Although not shown, the structure is such that the cooling water can pass therethrough.
【００１８】その後、放電電極３とロール型接地電極４
にマッチングボックス１を介して１３．５６ＭＨｚの高
周波を所定の電力で供給し、先ずＨｅ雰囲気下でグロー
プラズマを発生させた。次いで原料である有機珪素化合
物としてヘキサメチルジシロキサン（ＨＭＤＳＯ）を使
用し、所定量のＨｅ及びＯ2 ガスとともに７６０Ｔｏｒ
ｒの圧力下に、スリット部２２からプラズマ内に供給し
た。液体であるＨＭＤＳＯの供給はＨＭＤＳＯを入れた
容器１２にキャリアガス導入管１５からＨｅガスを導入
してバブリングさせ、このＨｅガスをキャリアガスとし
てＨＭＤＳＯを搬送させるようにした。処理中のＨｅガ
スとＯ2 ガスの比率はＨｅガス導入管１７からのＨｅガ
スとＯ2 ガス導入管１４からのＯ2 ガスにより調整し
た。また、フィルム処理の際のフィルム送り速度は０．
１〜０．５ｍ／ｍｉｎとした。Thereafter, the discharge electrode 3 and the roll type ground electrode 4
A high frequency of 13.56 MHz was supplied at a predetermined power through the matching box 1 to generate glow plasma in a He atmosphere. Next, hexamethyldisiloxane (HMDSO) is used as an organosilicon compound as a raw material, and 760 Torr with a predetermined amount of He and O 2 gas.
Under the pressure of r, the plasma was supplied from the slit portion 22 into the plasma. The liquid HMDSO was supplied by introducing He gas from the carrier gas introduction pipe 15 into the container 12 containing HMDSO and bubbling the HMDSO, and transporting the HMDSO using the He gas as a carrier gas. The ratio of the He gas and the O 2 gas during the treatment was adjusted by the He gas from the He gas introduction pipe 17 and the O 2 gas from the O 2 gas introduction pipe. In addition, the film feed speed during the film processing is 0.1.
1 to 0.5 m / min.
【００１９】前処理は次のように行った。すなわち、コ
ーティング処理を行う前の基材フィルム１６を、コーテ
ィングのときと同様にフィルム送りロール９に装着し、
張力調整用ロール１１、ロール型接地電極４、張力調整
用ロール１１を介してフィルム巻き取りロール１０に固
定し、チャンバ５内を０．１Ｔｏｒｒ程度まで十分排気
した。次いでＯ2 ガス導入管１４からＯ2 ガスを１０ミ
リリットル／ｍｉｎの流量で導入し、１３．５６ＭＨｚ
の高周波を１００Ｗの電力で供給しプラズマを発生さ
せ、フィルム送り速度０．５ｍ／ｍｉｎとして１秒間Ｏ
2 プラズマ処理した。The pretreatment was performed as follows. That is, the base film 16 before performing the coating treatment is mounted on the film feed roll 9 in the same manner as in the case of coating,
The film was fixed to the film take-up roll 10 via the tension adjusting roll 11, the roll-type ground electrode 4, and the tension adjusting roll 11, and the inside of the chamber 5 was sufficiently evacuated to about 0.1 Torr. Then O 2 gas O 2 gas introduction pipe 14 is introduced at a flow rate of 10 ml / min, 13.56 MHz
Is supplied at a power of 100 W to generate plasma, and the film is fed at a film feeding speed of 0.5 m / min for 1 second.
Two plasma treatments were performed.
【００２０】後処理は、コーティング処理後のフィルム
を前処理と同様の方法でＯ2 プラズマ処理することによ
って行った。なお本実施例においては、フィルム巻き取
りロール１０に巻き取られた前処理後のフィルムは、フ
ィルム送りロール９、フィルム巻き取りロール１０を逆
方向回転させて再度フィルム送りロール９に巻き取った
あと、前記によりコーティング処理を行った。また、後
処理も同様に行った。The post-treatment was performed by subjecting the film after the coating treatment to O 2 plasma treatment in the same manner as in the pre-treatment. In this embodiment, the pre-processed film wound on the film take-up roll 10 is wound on the film feed roll 9 again by rotating the film feed roll 9 and the film take-up roll 10 in the reverse direction. The coating process was performed as described above. Post-processing was also performed in the same manner.
【００２１】作製したガスバリア性フィルムの試料につ
いて、酸素透過率測定装置（ＭＯＣＯＮ社製、ＯＸ−Ｔ
ＲＡＮ１００）を使用して酸素透過量を測定し酸素ガス
バリア性を評価するとともに、ＪＩＳ−Ｚ０２０８に準
拠して水蒸気透過量の測定を行い水蒸気バリア性を評価
した。また、透明性については全光線透過率を測定し、
透過率が６０％以上のものを透明性◎、４０％以上６０
％未満のものを○、４０％未満のものを×として評価し
た。With respect to the sample of the produced gas barrier film, an oxygen permeability measuring device (OX-T, manufactured by MOCON) was used.
Using RAN100), the oxygen permeability was measured to evaluate the oxygen gas barrier properties, and the water vapor permeability was measured in accordance with JIS-Z0208 to evaluate the water vapor barrier properties. For transparency, measure the total light transmittance,
Those with a transmittance of 60% or more have a transparency of ◎, 40% or more and 60
% And less than 40% were evaluated as x.
【００２２】作製した試料の作製条件等を表３に、性能
評価試験結果を表４、図３及び図４に示す。表４の試料
Ｎｏ．０は比較のため未処理のＰＥＴフィルムのガスバ
リア性を示したものである。図３は前処理及び後処理の
効果を比較したものであり、Ｎｏ．１〜３を比較する
と、前処理を行わないでコーティング処理を施した場合
（Ｎｏ．１）、ガスバリア性の向上が認められるもの
の、その効果は小さく、前処理を行ったＮｏ．２と比較
するとガスバリア性が劣ることがわかる。このことか
ら、前処理がガスバリア性の向上に有効な処理であるこ
とが確認できる。また、後処理を施したＮｏ．３ではさ
らにガスバリア性が向上している。Table 3 shows the manufacturing conditions and the like of the manufactured samples, and Table 4 and FIGS. 3 and 4 show the results of the performance evaluation test. In Table 4, sample No. 0 indicates the gas barrier property of the untreated PET film for comparison. FIG. 3 compares the effects of pre-processing and post-processing. Comparing Nos. 1 to 3, when the coating treatment was performed without performing the pre-treatment (No. 1), although the gas barrier property was improved, the effect was small, and the effect was small. It is understood that the gas barrier property is inferior to that of No. 2. From this, it can be confirmed that the pretreatment is an effective treatment for improving the gas barrier property. In addition, No. In No. 3, the gas barrier properties are further improved.
【００２３】次に他の条件は一定として印加電力を変化
させた場合（Ｎｏ．３〜５）では、５０Ｗで処理を行っ
たＮｏ．４のガスバリア性が低いが、これは膜厚が２０
ｎｍと薄いためである。また、処理時間を変化させた例
（Ｎｏ．３、７、８）では、処理時間の長いＮｏ．７及
び８のガスバリア性が悪いが、これは膜厚が厚すぎて、
表面にクラックが生じやすくなったためである。Next, when the applied power was changed while keeping the other conditions constant (Nos. 3 to 5), No. 3 was processed at 50 W. 4 has a low gas barrier property,
This is because it is as thin as nm. In the example in which the processing time was changed (Nos. 3, 7, and 8), No. 3 having a long processing time was used. Gas barrier properties of 7 and 8 are bad, but this is too thick,
This is because cracks are easily generated on the surface.
【００２４】次に、導入するＯ2 ガス流量を変化させた
場合（Ｎｏ．３、９、１０）、ガス流量の変化によって
バリア性に大きな変化は見られず、いずれも良好なガス
バリア性を示した。図４はＮｏ．３〜１０の試料につい
て、コーティングした膜厚に対してＯ2 及び水蒸気のバ
リア性を比較したものである。膜厚が４０〜６０ｎｍの
場合、良好なガスバリア性を示しているが、膜厚がそれ
以上厚くなるとバリア性が低下する。これは膜が厚いた
め表面にクラックを生じやすくなりバリア性が低下する
ためであると思われる。以上の結果より、ガスバリア性
が効果的に作用する膜厚みは４０〜６０ｎｍ近辺であ
る。Next, when the flow rate of the introduced O 2 gas was changed (Nos. 3, 9, and 10), no significant change was observed in the barrier property due to the change in the gas flow rate, and all showed good gas barrier properties. Was. FIG. About 3-10 samples, a comparison of the O 2 and barrier properties of water vapor with respect to the coated film thickness. When the film thickness is 40 to 60 nm, good gas barrier properties are exhibited, but when the film thickness is further increased, the barrier properties are reduced. This is presumably because the film is thick and cracks easily occur on the surface, and the barrier property is reduced. From the above results, the thickness of the film on which the gas barrier property works effectively is around 40 to 60 nm.
【００２５】[0025]
【表３】 [Table 3]
【００２６】[0026]
【表４】 [Table 4]
【００２７】[0027]
【発明の効果】本発明の方法によれば、高分子フィルム
上に液体の有機珪素化合物を原料として大気圧及びその
近傍の圧力で発生させたグロープラズマを用いたＣＶＤ
法により酸化珪素膜を比較的簡単に操作性よく形成させ
ることができる。また、適切な前処理及び／又は後処理
を行うことにより、さらにガスバリア性に優れたフィル
ムを製造することが可能であり、これらのフィルムのガ
スバリア性は時間経過による性能の低下もみられない。According to the method of the present invention, CVD using a glow plasma generated on a polymer film at atmospheric pressure or a pressure near the atmospheric pressure using a liquid organosilicon compound as a raw material.
By the method, a silicon oxide film can be relatively easily formed with good operability. In addition, by performing appropriate pre-treatment and / or post-treatment, it is possible to produce films having more excellent gas barrier properties, and the gas barrier properties of these films do not show a decrease in performance over time.
【図１】本発明方法を実施するための大気圧プラズマ処
理装置の概要を示す説明図。FIG. 1 is an explanatory view showing an outline of an atmospheric pressure plasma processing apparatus for carrying out a method of the present invention.
【図２】図１の大気圧プラズマ処理装置のプラズマ処理
部の拡大図。FIG. 2 is an enlarged view of a plasma processing unit of the atmospheric pressure plasma processing apparatus of FIG.
【図３】実施例における前処理及び後処理の有無とガス
バリア性との関係を示す図。FIG. 3 is a diagram showing the relationship between the presence or absence of pre-processing and post-processing and gas barrier properties in an example.
【図４】実施例におけるコーティング膜厚とガスバリア
性との関係を示す図。FIG. 4 is a diagram showing a relationship between a coating film thickness and gas barrier properties in Examples.
Claims (4)
温度域において液体である有機珪素化合物を原料とし
て、６００〜１５２０Ｔｏｒｒの圧力下で発生するプラ
ズマを用いたＣＶＤ法により、ＳｉＯｘ（ｘ＝１．０〜
２．０）で表される酸化珪素を主成分とする薄膜を形成
させることを特徴とするガスバリア性フィルムの製造方
法。An SiOx (x = x) film is formed on a polymer film by a CVD method using a plasma generated under a pressure of 600 to 1520 Torr using an organic silicon compound which is a liquid in a temperature range of 20 to 150 ° C. as a raw material. 1.0-
2.0) A method for producing a gas barrier film, comprising forming a thin film containing silicon oxide as a main component represented by the formula (2).
るに先立ち、高分子フィルムに、該高分子フィルム表面
に付着した汚れ物質の除去、表面活性化のための前処理
を施すことを特徴とする請求項１に記載のガスバリア性
フィルムの製造方法。2. Prior to forming a thin film containing silicon oxide as a main component, the polymer film is subjected to a pretreatment for removing dirt attached to the surface of the polymer film and activating the surface. The method for producing a gas barrier film according to claim 1.
た後に、後処理としてＯ2 プラズマ処理を行うことを特
徴とする請求項１又は２に記載のガスバリア性フィルム
の製造方法。3. The method for producing a gas barrier film according to claim 1, wherein an O 2 plasma treatment is performed as a post-treatment after forming the thin film containing silicon oxide as a main component.
であることを特徴とする請求項１〜３のいずれか１項に
記載のガスバリア性フィルムの製造方法。4. The method for producing a gas barrier film according to claim 1, wherein the thickness of the thin film is in a range of 5 to 200 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05946498A JP4012620B2 (en) | 1998-03-11 | 1998-03-11 | Method for producing gas barrier film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05946498A JP4012620B2 (en) | 1998-03-11 | 1998-03-11 | Method for producing gas barrier film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11256338A true JPH11256338A (en) | 1999-09-21 |
| JP4012620B2 JP4012620B2 (en) | 2007-11-21 |
Family
ID=13114074
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05946498A Expired - Fee Related JP4012620B2 (en) | 1998-03-11 | 1998-03-11 | Method for producing gas barrier film |
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| Country | Link |
|---|---|
| JP (1) | JP4012620B2 (en) |
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| JP2001271167A (en) * | 2000-03-24 | 2001-10-02 | Okura Ind Co Ltd | Method for depositing zinc oxide thin film |
| WO2003094256A3 (en) * | 2002-04-30 | 2004-04-01 | Vitex Systems Inc | Barrier coatings and methods of making same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001271167A (en) * | 2000-03-24 | 2001-10-02 | Okura Ind Co Ltd | Method for depositing zinc oxide thin film |
| KR100438940B1 (en) * | 2001-10-12 | 2004-07-03 | 주식회사 엘지이아이 | Anti-corrosion treatment method of metal using plasma |
| KR100438941B1 (en) * | 2001-10-12 | 2004-07-03 | 주식회사 엘지이아이 | Multi-layer deposition method using plasma |
| EP1493311A1 (en) * | 2002-04-10 | 2005-01-05 | Dow Corning Ireland Limited | Gel and powder making |
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| JP2010013735A (en) * | 2009-09-29 | 2010-01-21 | Konica Minolta Holdings Inc | Method for producing resin film, and organic electroluminescence element using the resin film |
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| US9763345B2 (en) | 2011-03-30 | 2017-09-12 | Lintec Corporation | Gas barrier laminated body, method for producing same, member for electronic device, and electronic device |
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